Arylides of hydroxynaphthoic acids



to light and washing may be produced by coupling ?atented Sept. 5, 1933 1,925,801 7 v ARYLIDES or HYDROXYNAPHTHOIC ACIDS Ernest F. Grether, lvlfidland, Mich, assignor to The Dow Chemical Company, a corporation of Michigan lvlidland, Mi n,

N0 Drawing. Original application February .2, y 1931, Serial No. 513,055. Divided and this ap-' plication April 18, 1932. Serial No. 606,077

6 Claims. (Cl. 260-124) The present invention concerns new arylides of hydroxynaphthoic acids from which azo dyes of the direct developed type may be formed bycoupling diazotized or polyazotized aromatic amines therewith. The present invention particularly concerns the 3-halo-4-phenoXy-anilides vof hydroxynaphthoic acids, and the invention more particularly concerns such anilides of 2.3-hydroxynaphthoic'acid. I i

It is well known that azo dyes which are fast diazotized aromatic amines with arylides such as naphthol AS, the latter being the anilideof 2.3 hydroxynaphthoic acid. In a co-pending appli cation, Serial No. 513,055, filed February 2, 1931, of which the present application is a division, I have disclosed that the 3-halo-4-phenoxyanilides of hydroxynaphthoic acid may be coupled with diazotized aromatic amines to form a new class of valuable azo dyes, and have claimed the dyes so formed. I am claiming herein the new arylides 'from which such dyes were formed, said arylides having the general formula;-

wherein X represents a halogen.

The present invention, then, consists of the new products, together with the methods of preparing the same, hereinafter fully described and particularly pointed out in the claims, the following description setting forth but several of the various ways in which the principle of the invention may be used.

An arylide of the present class may be prepared through reacting a 3-halo-4-phenoxy-aniline with a hydroxynaphthoyl chloride, e. g. 2.3-hydroxynaphthoyl chloride, or with the free hydroxy-naphthoic acid in the presence of a condensing agent, e. g. phosphorous trichloride, and in the presence of a substantiallyinert solvent, such as toluene, xylene, etc. Y

The follownig specific example illustrates one of the several ways in which the invention may be utilized:-

alcohol, filtering from unreacted 3-chloro-4- Example The 3 cliloroi-phenoiiy-anil ide or 2.3-hy-. droxynaphthoic. acid Was prepared by heating under reflux substantially e'quimolec'ular quantir ties of 3-chloroi-phenoxy-aniline and 2.3-hydroxynaphthoic acid, in the presence of about 13 per cent of their combinedwe'ight (slightly more than one-third of a molecular equivalent) of phosphorous trichloride, withs't irring', and in the 0 presence of sufiicient toluene'to permit such stirring, for a period of from'3 to 5 hours, Thereaction product was neutralized by adding an ex:- cess of sodium carbonate and the toluene removed by distilling with steam. The aqueous residue, containing the arylide product in suspensionther'ein, was filtered and the residue washed with water." The product was then purified by dissolving the same in dilute, 1 to 2 per cent, caustic alkali solution, preferably in the presence of 10 phenoXy-aniline and precipitating by acidification of the alkaline solution. The anilide so obtained, having a melting point of approximately 210-212 C., is a fine powder, nearly white in 775 color. It has probably the formula;

etc., in place of phosphorous trichloride, as de- 0 scribed; Other hydroxynaphthoic acids, e. g.

1.2-hydroxynaphthoic acid, etc., may be condensed with a 3-halo-4-phenoxy-aniline, to form an arylide of the hydroxynaphthoic acid. Furv thermore, other 3-halo-4-phenoxy-anilines, e. g. 3-bromo-4-phenoxy-aniline, may be condensed with'a hydroxynaphthoic acid to form an arylide of the latter, the procedure involved being similar to that already described.

wherein X represents a halogengrouprthe step which consists in condensing a 3-halo-4-phenoxyaniline with an ortho hydroxynaphthoic acid in the presence of a condensing agent.

2. In a method of makinganarylide having the general formula;-

wherein X represents a halogen group, the step which consists in condensing a 3-ha1o-4-phenOxy-aniline with 2.3-hydroxynaphthoic acid in the presence of a condensing agent selected from {the group consisting of phosphorous trichloride, phosphorous pentoxide, phosphorous oxychloride,

and thionyl chloride. I

3.' In a methodof making the 3 -chlorolphenoxy-anilide of 2.3-hydr0xynaphthoic acid,

having probably the formula the step which consists in condensing 3-chloro- 4-phenoxy-aniline with 2.3-hydroxynaphthoic acid in the presence of phosphorous trichloride as a condensing agent.

l. As a new compound, an arylide of an ortho hydroxynaphthoic acid having the general forwherein X represents a halogen group.

5. As a new compound, an arylide of 2.3-hydroxynaphthoic acid having the general formula;

OH n

wherein X represents a halogen group.

6. As a new compound, the 3-chloro-4-phenoXy-anilide of 2.3 hydroxynaphthoic acid having probably the formula j OH I 01 r and having a melting point of approximately 210-212 C.

ERNEST F. GRETHER. 

